WO2009110971A2 - Procédé de conversion d’alcools aliphatiques multifonctionnels - Google Patents

Procédé de conversion d’alcools aliphatiques multifonctionnels Download PDF

Info

Publication number
WO2009110971A2
WO2009110971A2 PCT/US2009/001163 US2009001163W WO2009110971A2 WO 2009110971 A2 WO2009110971 A2 WO 2009110971A2 US 2009001163 W US2009001163 W US 2009001163W WO 2009110971 A2 WO2009110971 A2 WO 2009110971A2
Authority
WO
WIPO (PCT)
Prior art keywords
epichlorohydrin
polyol
alcohols
pentaerythritol
hydroxyl groups
Prior art date
Application number
PCT/US2009/001163
Other languages
English (en)
Other versions
WO2009110971A3 (fr
Inventor
Veera Reddy Pulgam
Sonke Svenson
Michael A. Zhuravel
Original Assignee
Dendritic Nanotechnologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dendritic Nanotechnologies, Inc. filed Critical Dendritic Nanotechnologies, Inc.
Publication of WO2009110971A2 publication Critical patent/WO2009110971A2/fr
Publication of WO2009110971A3 publication Critical patent/WO2009110971A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

Definitions

  • This invention relates to the field of converting multifunctional organic aliphatic alcohols by a process to modify their functionality. Additionally, this invention concerns the use of converted multifunctional aliphatic alcohols for the preparation of industrial formulations with the intent to improve their specific performance such as increased cross- linking density, tensile strength, scratch resistance, waterfastness, cure speed, and/or durability. These compounds have a variety of uses such as additives for inks and surface modifications.
  • Base reagents applied to the process were sodium hydroxide or potassium hydroxide utilized as a solution in water or in a solid state, for example, pulverized.
  • Epichlorohydrin was used in 1-3 mols per hydroxyl equivalent but at least more than 1 A mol per hydroxyl equivalent.
  • the reaction temperatures could vary between room temperature and boiling temperature of the reaction mixture.
  • the base reagent was added continuously at the rate it was consumed. Water formed during the reaction was continuously removed, while epichlorohydrin that had distilled over was returned to the reaction mixture.
  • the process always resulted in product mixtures of alcohols containing at least one epoxy group.
  • the content of epoxy groups was dependent on the reaction conditions, especially on the molecular ratio of epichlorohydrin to the number of hydroxyl groups per alcohol molecule.
  • pentaerythritol 136 parts, 1 mol
  • 30% aqueous caustic soda solution 533 parts
  • the reaction mixture was kept at 100-115°C for about one hour, while water was distilled from the mixture and epichlorohydrin that had distilled off was retuned to the reaction mixture.
  • the reaction mixture was allowed to cool to room temperature.
  • the mixture was filtered, the salt washed with epichlorohydrin, and the wash combined with the reaction solution.
  • Claimed is a single-stage process for the manufacture of a product consisting substantially of polyethers containing at least one epoxy group, which includes continuously distilling off water and epichlorohydrin from the reaction mixture, separating the distilled products and returning only the epichlorohydrin to the reaction mixture.
  • Aromatic Alcohols US Patent 3,244,731 (1966) discloses the conversions of alcohols containing an aromatic moiety into epoxides using epichlorohydrin, glycerol dichlorohydrin or other halohydrins or epihalohydrins in the presence of suitable bases, following the single-stage process.
  • Epichlorohydrin was added in excess of the stoichiometric quantity to prevent polymerization between remaining alcohol groups and already converted epoxy groups.
  • the base reagents sodium hydroxide or potassium hydroxide (1-1.5 equiv. per OH) were added as solid, suspension, or aqueous solution. Reaction temperatures were 20-180 0 C, preferably between 40 0 C and the boiling point of the mixture. Salt formed during the reaction was removed by filtration, and excess epichlorohydrin was removed by vacuum distillation.
  • Dioxane was distilled off after stage one to avoid contamination of dioxane with water formed during the hydrogen chloride removal using sodium hydroxide. Mixtures of organic solvents having a boiling point higher than 70 0 C together with dioxane could be used instead of neat dioxane. Pentaerythritol yielded product mixtures containing molecules with different amounts of epoxy groups, dimers, and some compounds carrying chloro atoms.
  • polyols were dispersed in solvents such as toluene, 1,4-xylene, 1,3-xylene, 1,2-xylene, acetone, methylethylketone, methyliso- butylketone, carbon tetrachloride, chloroform, 1,2-dichlorethene, n-hexane, or cyclohexane.
  • solvents such as toluene, 1,4-xylene, 1,3-xylene, 1,2-xylene, acetone, methylethylketone, methyliso- butylketone, carbon tetrachloride, chloroform, 1,2-dichlorethene, n-hexane, or cyclohexane.
  • the polyols were pulverized to particle sizes of 200 ⁇ m, preferable 40 ⁇ m.
  • Xylene technical quality
  • British Patent 2,151,637 (1985) (see also French Patent 2,555,184 and German Patent 3,442,232) disclosed reacting an acrylic prepolymer containing an aliphatic, acyclic, aromatic or heterocyclic residue with an epoxy compound derived from diglycerol, trimethylolpropane, or pentaerythritol. It was taught that polyepoxy compounds used in this process could be made from the polyol and epichlorohydrin. No specific conditions or examples were provided. Gu et al. [Synthesis Communications 649 (1985)] reported the conversion of linear diols into linear diepoxides using epichlorohydrin as the reactant and main solvent, mixed with some water as co-solvent.
  • PETGE was prepared from pentaerythritol and epichlorohydrin following the process reported by Kida et al., except the final purification of PETGE was done by column chromatography using acetone/toluene (1:9) as eluent. The isolated yield of PETGE was 37%. The presence of an unidentified by-product was reported.
  • Example B In the portion Starting Materials, Example B [erroneously labeled as "according to Mitsuo et al., Synthesis 487 (1993)], the process was repeated at lower temperature. Pentaerythritol (13.6 g, 0.4 mol) was mixed with dimethyl sulfoxide (100 mL), and potassium hydroxide (52.7 g, 0.8 mol; 2 equiv. per OH) was added. Then the mixture was cooled to 15-2O 0 C and epichlorohydrin (110.4 g or 93.55 mL, 1.2 mol; 3 equiv. per OH) was added dropwise at this temperature. After warming to room temperature, the mixture was stirred overnight.
  • TCL Thin layer chromatography
  • the glycidyl ethers with reduced chlorine content were made for use in electrical and electronic materials, coating field, and others by reacting alcohols with epichlorohydrin in the presence of a pulverized solid alkali metal hydroxide added into the reaction mixture.
  • Alcohols especially polyhydric alcohol, e.g. 1,6-hexyleneglycol
  • a solid alkali metal hydroxide preferably sodium hydroxide used in one form as grain, flake or powder
  • Pulverization of the base reagent was important to provide the high-purity aliphatic glycidyl ethers.
  • the process is based on the two-stage process using a Lewis acid ⁇ i.e., boron trifluoride etherate) in the first stage.
  • This invention describes a single-stage process for the conversion of aliphatic polyol alcohols into epoxy compounds of high product purity and uniformity. Particularly desired are the conversion of triol and tetrol alcohols (which have given either low yields or product mixtures containing molecules with varying degrees of conversion of alcohol to epoxy groups using previously disclosed processes) have been converted into their respective epoxides in high yield and product uniformity.
  • This invention concerns a single-stage process for converting polyol alcohols having at least 3 hydroxyl groups ⁇ e.g., from 3-10 hydroxyl groups, especially 3 or 4 hydroxyl groups) into their epoxides by the following steps:
  • step 2 2. adding the polyol having at least 3 hydroxyl groups to the solvent of step 1;
  • step 2 3. adding freshly ground KOH to the well stirred solution of step 2 while maintaining the temperature from about 10 to about 25°C;
  • step 4 4. adding EPI, about 3 equiv. of EPI per hydroxyl, slowly to the solution of step 3 such that the temperature range of step 3 can be maintained;
  • Alkyl means any number of carbon atoms for the term that is used, whether linear or branched, alone or part of another term such as alkyl substituted, alkylaryl, cycloalkyl, heterocyclic moieties, and others; typically from Ci-Cioo, with C 1 -CsO preferred and C 1 -C 25 most preferred.
  • alkene and alkyne are defined broadly; typically from C 2 -C 2 Oo, with C 2 -Ci 0 O preferred, amu means atomic mass units brine means a saturated aqueous solution of sodium chloride
  • DCM means dichloromethane DI means deionized water (18.2 M ⁇ ) diol means an alcohol molecule containing two hydroxyl (OH) groups.
  • DMSO dimethylsulfoxide
  • Acros Organics equiv. means equivalent(s)
  • EPI epichlorohydrin epoxy means a cyclic ether group in which one oxygen atom is connected to two adjacent carbon atoms in such a way that a strained ring is formed. Epoxy is also referred to herein as glycidyl ether.
  • FT-IR means Fourier Transform Infrared Spectroscopy
  • g means gram(s)
  • glycidyl ether means a cyclic ether group in which one oxygen atom is connected to two adjacent carbon atoms in the way that a strained ring is formed.
  • Glycidyl ether is also referred to as epoxy or epoxy group, h means hour(s)
  • HPLC means high pressure liquid chromatography
  • KOH means potassium hydroxide
  • pellets by Aldrich L means liter(s)
  • MALDI-TOF matrix-assisted laser desorption ionization time of flight mass spectroscopy
  • MeOH means methanol; 99.8% by Aldrich mg means milligram(s) min. means minute(s) mL means milliter(s)
  • NaOH sodium hydroxide
  • NMR nuclear magnetic resonance
  • PEPE pentaerythritol propargyl ether
  • PETGE means pentaerythritol tetraglycidyl ether
  • PPT pentaerythritol propargyl triglycidyl ether polyol means an alcohol molecule containing at least two or more hydroxyl (OH) groups.
  • Rf means relative flow in TLC
  • RT means ambient temperature or room temperature, about 20-25 0 C
  • SEC size exclusion chromatography tetrol means an alcohol molecule containing four hydroxyl (OH) groups.
  • TLC means thin layer chromatography
  • TMPTGE trimethylolpropane triglycidyl ether triol means an alcohol molecule containing three hydroxyl (OH) groups.
  • UV/vis means ultraviolet and visible spectroscopy
  • 2006/115547 illustrates a potential mixture generated by conversion of pentaerythritol (1), showing the perfect, completely converted tetra-epoxide (ID), an incompletely converted alcohol (TV) (i.e., the tri-epoxy monoalcohol), and a dimer molecule (V).
  • ID perfect, completely converted tetra-epoxide
  • TV incompletely converted alcohol
  • V dimer molecule
  • the corresponding mono-epoxide and di-epoxide are being formed as well, leading to product mixtures with low epoxy-equivalent (ep.-eq.) per kilogram.
  • the present single-stage process of this invention makes several important improvements over previously known processes, which improvements result in high yield and high product uniformity.
  • the present process concerns a single-stage process for converting polyol alcohols having at least 3 hydroxyl groups (e.g., from 3-10 hydroxyl groups, especially 3 or 4 hydroxyl groups) into their epoxides by the following steps:
  • step 2 2. adding the polyol having at least 3 hydroxyl groups to the solution of step 1; 3. adding freshly ground KOH to the well stirred solution of step 2 while maintaining the temperature from about 10 to about 25°C;
  • step 4 4. adding EPI, about 3 equiv. of EPI per hydroxyl, slowly to the solution of step 3 such that the temperature range of step 3 can be maintained;
  • Ri means hydrogen, hydroxyl, methyl, or propargyl (HCsC-CH 2 -O-);
  • R 2 means hydrogen, methyl, epoxy or propargyl (HC ⁇ C-CH 2 -O).
  • R 2 means hydrogen, methyl, epoxy or propargyl (HC ⁇ C-CH 2 -O).
  • EPI addition needs to be done slowly so that no or little free EPI remains in the reaction mixture when the next addition of EPI is done.
  • this EPI addition is preferably done dropwise. EPI is added in excess, e.g., about 3-fold excess per hydroxyl group.
  • chain lengths e.g., between 2 and 10 carbon atoms
  • neopentylglycol e.g., glycerin
  • trimethylolpropane dipentaerythritol
  • mannitol mannitol
  • These alcohols are just a few examples provided to illustrate
  • Polyepoxides made via this present process can find applications as materials or additives for ultraviolet light (UV) or electronic beam (EB) cured inkjet inks and coatings to increase tensile strength, waterfastness, and/or scratch resistance.
  • these polyepoxides can be used as materials or additives for electrical laminates, elastomers, and thin-films to increase cross-linking density, lower conductivity, and lower chlorine content.
  • they can be used as materials or additives for paper chemicals, textile finishing agents, surface coatings, and inkjet inks to increase cure speed and/or reduce cure time, increase tensile strength, improve scratch resistance, and/or enhance durability.
  • these polyepoxides can be used as resin materials for electrical boards, circuits and textile surfaces to improve adhesion and/or increase tensile strength.
  • the reagents and solvents used were purchased from Aldrich or as indicated in the Glossary or made as described herein.
  • MALDI-TOF mass spectrometry was performed on a Bruker Autoflex-LRF Mass Spectrometer.
  • Example 1 Synthesis of Pentaerythritol Tetraglycidyl Ether (PETGE) from Pentaerythritol and Epichlorohydrin (EPI) (small scale).
  • PETGE Pentaerythritol Tetraglycidyl Ether
  • EPI Epichlorohydrin
  • Pentaerythritol (13.6 g, 400 mmol) and 100 mL of DMSO were mixed for 15 min. at 24°C. Then KOH (85%) (52.5 g, 800 mmol, 2 equiv. per OH; finely ground with a blender just prior to addition to the mixture) was added at once, and the mixture stirred for another 15 min. at 24°C. The reaction mixture was stirred vigorously with a mechanical stirrer and cooled to 15-20 0 C with an ice bath. EPI (110.4 g, 1.2 mol, 3 equiv. per OH) was added dropwise over 1.5 h using a pressure-equalizing funnel.
  • reaction mixture was allowed to warm to 24°C, and stirring continued for 16 h. During this time the mixture became a light brownish color.
  • the reaction mixture was extracted between equal amounts of water and DCM. DCM fraction was dried over sodium sulfate, filtered, and volatile fractions of DCM were removed by rotary evaporation (75°C water bath temperature). The crude residue was further purified by Kugelrohr distillation at 180 0 C, giving a pale yellow liquid (32.7 g, 90.8% of theoretical yield).
  • the product was analyzed by proton and carbon NMR, and it was found that the desired PETGE product was the major product with 85-90% purity, base on integrals for epoxy proton NMR signals
  • PETGE Pentaerythritol Tetraglycidyl Ether
  • EPI Epichlorohydrin
  • Pentaerythritol (68 g, 0.5 mol) and DMSO (500 mL) were mixed and the mixture stirred for 15 min. at RT.
  • KOH 85-90%) was powdered with blender just prior to use and KOH (263.5 g, 4.0 mol, 2 equiv. per OH) was added and the mixture stirred for 20 min. at RT.
  • the reaction mixture was then cooled to 10-15 0 C with ice-cold water. It takes 15-20 min. to get desired temperature.
  • EPI 552.0 g or 467.75 mL, 6.0 mol; 3 equiv. per OH was added dropwise over a period of 4 h.
  • reaction temperature After adding 1/3 of EPI, the reaction temperature increased but was controlled by vigorous stirring, proper cooling, and slow addition of the remaining EPI.
  • the reaction mixture slowly changed to a brownish color.
  • the mixture was allowed to warm to RT, while stirring continued for 18 h. After that time the mixture was warmed to 30 0 C with hot water for 1 h. It is necessary to warm the reaction to prescribed temperature to convert the tri-epoxy by-product to the desired tetra-epoxy product, PETGE.
  • the reaction mixture was cooled back to 15°C with ice-cold water. Quenching with water is an exothermic reaction and temperature rises to 17-18°C after adding first portion of the water. Temperature was brought back to 10 0 C before adding next portion of the water.
  • the reaction mixture was diluted with DCM (300 mL), and quenched with water (550 mL). The mixture was transferred into a separatory funnel, diluted further with water (1.5 L) and DCM (500 mL), mixed thoroughly, and allowed to settle over 10-15 min. The bottom organic layer was separated, and the aqueous phase extracted with DCM (2x500 mL). The combined organic layers were washed with water (2x500 mL), dried over Na 2 SO 4 (75 g) and passed through a CeliteTM bed to remove some solid particles. Solvent was removed by rotary evaporation (45°C water bath temperature), followed by removal of other low boiling side products and excess EPI by increasing the water bath temperature to 75°C.
  • Pentaerythritol propargyl ether 1 (5.11 g, 29.36 mmol) and DMSO (30 mL) were mixed and the mixture stirred for 15 min. at RT. Powdered KOH (11.6 g, 176.2 mmol; 2 equiv. per OH; 85%, ground with a blender) was added and the mixture stirred for 20 min. at RT. The reaction mixture was then cooled to 10 0 C with ice-bath. EPI (24.31 g or 20.6 mL, 264.24 mmol; 3 equiv. per OH) was added dropwise over a period of 75 min. After complete addition, the mixture was allowed to warm to RT, while stirring continued for 18 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé à une étape pour la préparation d’époxydes multifonctionnels qui comprennent au moins trois groupes hydroxyles. Le procédé selon l’invention utilise de l’épichlorhydrine en présence de KOH fraîchement broyé, à une température comprise entre 10 et 25 °C.
PCT/US2009/001163 2008-02-26 2009-02-25 Procédé de conversion d’alcools aliphatiques multifonctionnels WO2009110971A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6712108P 2008-02-26 2008-02-26
US61/067,121 2008-02-26

Publications (2)

Publication Number Publication Date
WO2009110971A2 true WO2009110971A2 (fr) 2009-09-11
WO2009110971A3 WO2009110971A3 (fr) 2010-01-21

Family

ID=41056509

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/001163 WO2009110971A2 (fr) 2008-02-26 2009-02-25 Procédé de conversion d’alcools aliphatiques multifonctionnels

Country Status (1)

Country Link
WO (1) WO2009110971A2 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2898349A (en) * 1953-03-25 1959-08-04 Ciba Ltd Process for the manufacture of reaction products of epichlorhydrin and polyhydric alcohols
US5710290A (en) * 1996-10-21 1998-01-20 The Dow Chemical Company Functionalized cycloaliphatic nitrile oxides
US6946502B1 (en) * 1999-01-18 2005-09-20 Dynea Chemicals Oy Paint compositions
US20070100023A1 (en) * 2005-10-31 2007-05-03 Burns Elizabeth G Modified colorants and inkjet ink compositions comprising modified colorants
US20070119745A1 (en) * 2004-02-19 2007-05-31 Martin Vogel Multi-component kit for fixing purposes and its use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2898349A (en) * 1953-03-25 1959-08-04 Ciba Ltd Process for the manufacture of reaction products of epichlorhydrin and polyhydric alcohols
US5710290A (en) * 1996-10-21 1998-01-20 The Dow Chemical Company Functionalized cycloaliphatic nitrile oxides
US6946502B1 (en) * 1999-01-18 2005-09-20 Dynea Chemicals Oy Paint compositions
US20070119745A1 (en) * 2004-02-19 2007-05-31 Martin Vogel Multi-component kit for fixing purposes and its use
US20070100023A1 (en) * 2005-10-31 2007-05-03 Burns Elizabeth G Modified colorants and inkjet ink compositions comprising modified colorants

Also Published As

Publication number Publication date
WO2009110971A3 (fr) 2010-01-21

Similar Documents

Publication Publication Date Title
EP0150850B1 (fr) Composé polyéther et procédé pour leur production
EP0022073B1 (fr) Ethers di-glycidyliques d'alcools di-secondaires, leur préparation et leur utilisation
JPH07119269B2 (ja) エポキシ樹脂
US20020045707A1 (en) Process for manufacturing a hydroxyester derivative intermediate and epoxy resins prepared therefrom
Makwana et al. Cardol: Cashew nut shell liquid (CNSL)-derived starting material for the preparation of partially bio-based epoxy resins
EP3567065A1 (fr) Procédé de préparation de composé époxy doté d'un groupe d'alkoxysilyles
KR20150088612A (ko) 에폭시 반응성 희석제의 제조방법
JP2007284518A (ja) エポキシ樹脂組成物、その硬化物、新規エポキシ化合物及びこの製造方法
EP4148047A1 (fr) Résine époxy
KR20160101935A (ko) 에폭시 수지, 그 제조 방법, 에폭시 수지 조성물 및 그 경화물
WO2009110971A2 (fr) Procédé de conversion d’alcools aliphatiques multifonctionnels
Zhang et al. Synthesis and characterization of a novel cycloaliphatic epoxy resin starting from dicyclopentadiene
JP2016199472A (ja) ビスフェノキシフェノールフルオレン骨格を有するエポキシ樹脂
CN111621002B (zh) 一种非离子型水性环氧树脂固化剂及其制备方法
JP2016020308A (ja) 環状リン含有エポキシ化合物の製造方法
KR20020031316A (ko) 에폭시 수지 조성물 및 그의 제조 방법
JP5885126B2 (ja) エポキシ化合物及びその製造方法ならびにエポキシ樹脂組成物及びその硬化物
JP3072113B2 (ja) ポリエーテル化合物、エポキシ化合物およびエポキシ化合物からなる組成物
JPS63234028A (ja) ポリエ−テル化合物
AU2017301100A1 (en) Epoxy resin
US3288761A (en) Curable mistures of diepoxy compounds and dicarboxylic acid anhydrides
JP3014404B2 (ja) ポリエーテル化合物およびエポキシ化合物
JP4004787B2 (ja) フェノール樹脂、エポキシ樹脂、その製造方法及び半導体封止材用樹脂組成物
JP4158137B2 (ja) エポキシ樹脂組成物及びその硬化物。
JPH06306162A (ja) ハロゲン化合物の製造法および合成樹脂用難燃剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09717917

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09717917

Country of ref document: EP

Kind code of ref document: A2